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Unite tcs ANTIFOGGANTS FOR REVERSAL COLOR DEVELOPMENT Catherine MarilynSpath, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester,N.Y., a corporation of New Jersey N Drawing. Application January 24,1957 Serial No. 635,944

Claims. (Cl. 96-56) the blue-sensitive and green-sensitive layers is afilter layer for absorbing blue radiation which may be transmittedthrough the blue-sensitive layer. The multi-layer coating can also haveother interlayers for specialized purposes. Such multi-layer materialshave been previously described in the prior art, such as Mannes et al.US. Patent 2,252,718, issued August 19, 1941.

Color materials of the type employed in the instant invention are thoseintended primarily for reversal processes, wherein the exposed materialis given a conventional black-and-white development, followed by areversal exposure, or exposures, and color development.

The color materials used in my invention comprise emulsions which cancontain color-forming materials or couplers, or these color couplers canbe used instead in the color developers.

It is, therefore, an object of my invention to provide improveddevelopers for reversal color photography. Another object is to providea method of inhibiting color fog and increasing the maximum colordensity. Other objects will become apparent from a consideration of thefollowing examples and description.

During the black-and-white development of multi-layer color materials,fog centers are introduced into the unexposed regions, and upon reversalexposure and subsequent color development, these unexposed areas havedeposited therein coupled color-forming materials, resulting in severeloss of color quality. For example, in processing color materials of theKodachrome type, color developer containing a cyan coupler results notonly in development of the red-sensitive layer, but also in developmentof cyan fog in the blueand green-sensitive layers. This fog isparticularly severe in emulsions which contain conventional chemicalsensitizers, such as gold sensitizers, sulfur sensitizers, orpolyethyleneglycol type chemical sensitizers.

I have now found that such undesirable fog can be eliminated ormaterially reduced by adding an organic compound containing aformamidinothiomethyl substituent to one or more of the colordevelopers. These formamidinothiomethyl compounds decrease color fog inthe unexposed areas with no substantial loss of color density in theexposed areas. These compounds can be conveniently added to the colordeveloper, which may or may not contain a color coupler or color-formingcompound, depending upon the particular color material being atent O2,899,306 Patented Aug. 11, 1959 processed. It is to be understood thatmy invention comprises the use of color materials which may contain thecolor couplers or color-forming compounds either in the emulsions or inthe color developing solutions. Particular benefits have been obtainedwith color materials wherein the color couplers or color-formingmaterials are present in the color developing solutions.

It is known that a colored image can be formed by adding to certaincolor developing solutions, or by incorporating in the silver halideemulsion, a compound which couples during development with the oxidationproduct of the developing agent, thus forming a colored compound whichis deposited adjacent to the silver grains of the silver image duringsuch development. Such compound which is employed in conjunction withthe developing agent for the silver and which couples with the oxidationproduct of the developing agent during development is referred to as acolor-forming compound or coupler. Such compounds usually belong to oneof three widely known types, i.e., pyrazolone couplers, phenol couplers,or open-chain ketomethylene couplers. These couplers produce,respectively, magenta, cyan and yellow images.

The formamidinothiomethyl compounds useful in practicing my inventioninclude compounds represented by the following general formula:

v such as dimethylamino, diethylamino, etc., monoarylamino, such asphenylamino, tolylamino, etc., diarylamino, such as diphenylamino,ditolylamino, etc., heterocyclylamino, such as Z-thiazylamino,triazylarnino, etc), and R represents a carbalkoxyl group (e.g.,carbomethoxy, carb-ethoxyl, carbobutoxyl, etc., especially a carbalkoxylgroup containing from 2 to 5 carbon atoms), an alkyl group (e.g., ethyl,n-propyl, n-butyl, p-sulfoethyl, etc., especially an alkyl groupcontaining from 1 to 4 carbon atoms), a heterocyclyl group (e.g.,tetrazaindenyl, pyridyl, etc.), or an amido group (e.g., amidothiazylamido phenylamido2-formamidinothiomethyl-4-hydroxy-6-methy1-1,3,3a,7-

tetrazaindene Bis 2-formamidinothiomethyl-fi-methyl-l,3,3a,7-tetrazainden4-yl) sulfide HO3SCH2OH1S -i1=NH2S-thlouroniumethanesulfonate "\N) E-S-CH,C 0 CamS-carbethoxymethy1-1-pheny1-3- (4H-1,2,4-triazol-3-yl) isothlourea 0NET-H01 i S-Z- thiazylamidomethylthiouronium chloride 0 NH-HCI H2NgCHg-SCNH2 S-amidomethyltlfiouronium chloride (0) NH-HBr C4H9S-CNH2S-n-butylthionronium bromide The above formamidinothiomethyl compoundscan be prepared according to methods previously described in the art.See, for example, Knott et al. U.S. Patent 2,461,987, issued February15, 1949, and Tinker et a1. U.S. application Serial No. 515,785, filedJune 15, .1955 (now U.S. Patent 2,835,581, issued May 20, 1958). Furtherexamples describing the preparation of. these compounds are given below.

The formamidinothiomethyl compounds employed in the color developers ofmy invention can be utilized in various concentrations depending uponthe particular emulsions employed, the concentration of silver halidesin the emulsions, and the concentration of the developing agents in thedevelopers. In general, not less than about mg. per liter of developerof formamidinothiomethyl compound should be employed. The mostadvantageous concentration can be determined by developing a series oftest strips of silver halide emulsions wherein the concentration offormamidinothiomethyl compound is varied, as well as the concentrationof the developing agent. The usual addenda can be employed in thedevelopers, such as strongly alkaline agents, sodium carbonate,potassium carbonate, sodium hydroxide, etc., restraining agents, such aspotassium bromide, stain preventives, such as alkali metal sulfites,etc.

My invention is primarilydirected to the development of the ordinarilyemployed gelatino-silver-halide developing-out emulsions, e.g.,gelatino-silver-chloride,v -chlorobromide, -chloroiodide,-chlorobrorniodide, -bromide and -bromiodide developing-out emulsions.Whilethe results in the following examples were obtained usinggelatinosilver-bromiodide emulsions, excellent results can alsobeobtained using other silverhalide emulsions. These emulsions can becoated in the usual manner on any suitable support, e.g., glass,cellulose nitrate film, cellulose acetate film, polyvinyl acetal resinfilm, paper or metal.

Photographic silver halide emulsions useful in my invention can alsocontain such addendaas chemical sen- 75 sitizers, e.g., sulfursensitizers (e.g., allyl thiocarbamide, 'thiourea, allyl isothiocyanate,cystine, etc), various gold processes. Couplers or color-formingcompounds which are soluble in the strongly alkaline developingsolutions are well known to those skilled in the art. Typical couplersinclude the following:

COUPLERS FOR USE IN COLOR DEVELOPERS Cyan couplers:

1. S-benzenesulfonamino-l-naphthol 2.2,4-dichloro-5-benzenesulfamino-l-naphthol 3.2,4-dichloro-5-(p-toluenesulfamino)-1 naphthol 4. 5 (1,2,3,4tetrahydronaphthalene 6-sulf0namino) -1-naphthol 5. 2,4-dich1oro 5(4-bromodiphenyl 4 sulfonamino)-l-naphthol 6.o-(B-Naphthalenesulfonamino)-phenol 7. 5 (m nitrobenezenesulfonamino)l-naphthol 8. 5 (quinoline 5 sulfonamino) 1 naphthol (U.S. 2,362,598) 9.2-acetylarnino-5-methylpheno1 10. 2 benzoylamino-3,5 dimethylphenol 11.2 a-(p-tert. amylphenoxy)-n-butyrylamino-5- methylphenol 12. 2 a(p-tert. amylphenoxy)-n-butyrylamino4- chloro-S-methylphenol 13. 2(p'-tert. amylphenoxy p-benzoyl)amino-4- chloro-S-methylphenol 14. 2(4"-tert. amyl-3' phenoxybenzoylamino)- 3,5-dimethyl-1-phenol 15. 2phenylacetylamino-4-chloro S-methylphenol 16. 2 L benzoylamino 4 chloroS-methylphenol 17. 2 anilinoacetylamino-4-chloro S-methylphenol 18.2-{4'[oz-(4" tert. amylphenoxy) n-butyrylamino] benzoylamino}'4chloro-S-methylphenol 19. 2 {4-[3"-(4"-tert. amylphenoxy) benzoylamino]benzoylamino}-4-chloro-5-methylphenol 20. 2-p-nitrobenzoylamino 4 chloroS-methylphenol 21. 2 m-aminobenzoyl 4-chloro-5-methylphenol 22. 2acetamino-4-chloro-5-methylphenol 23. 2 (4'-sec.amylbenzamino)-4-chloro-5-methylphenol 24. 2-(4'- namyloxybenzamino)-4-chloro-5-methylphenol Magenta couplers:

25. 1 phenyl 3-acetylarnino-5-pyrazolone 26. l phenyl 3propionylamino-5-pyrazolone 27. 1 phenyl3-dichloroacetylamino-S-pyrazolone 28. 1 phenyl3-benzoylamino-S-pyrazolone 29. 1 phenyl 3-(m-aminobenzoyl) amino 5-pyrazolone hydrochloride 30. 1 phenyl 3 (diamylbenzoyl)amino 5pyrazclone 31. 1 phenyl-3-phenylcarbamylamino-5-pyrazolone 32. 1 phenyl3-phenoxyacetylamino-5-pyrazolone 33. 1 phenyl 3p-aminobenzoylamino-5pyrazolone 34. 1 phenyl r3-(o-carboxybenzoyl)amino-S-pyrazolone 35. 1 phenyl3-palmitylamino-5-pyrazolone 36. 1 -phenyl-3-(p-sec.amylbenzenesulfonylamino)- S-pyrazolone 37. 1 phenyl 3-[p-(p'-sec.amylbenzoyl)amin0- benzoylaminol -5-pyrazolone 38. 1-m-tolyl-3-[m-(B-pheny1propiony1)aminobenzoylamino] -5-pyrazolone 39. 1 m tolyl3-(2,4-di-tert. butyl-m-tolyloxyacetylamino)-5-pyrazolone 40. 1[p-(p-tert. butylphenoxy)phenyl] -3-[p-(benzoylamino) -benzoylamino]-5-pyrazolone 41. l-(p-tert. butylphenoxyphenyl) 3 (p-m-amyloxybenzoylamino) -5 -pyrazolone 42. 1-[p-(p'-tert. butylphenoxy)phenyl] 3(3,5-dimethoxybenzoyDamino-S-pyrazolone 43. 1-[p-(p'-tert.butylphenoxy)phenyl]-3 [m-(ptoluene-sulfonylamino)benzoylamino] -5pyrazolone 44. 1 [p-(3,5 dimethylphenoxy)phenyl]-3-(4-namyloxy-3 methylbenzoylamino) -5 -pyrazolone 45. 3-(p -'nitrophenoxyacetylamino)1-(2',4',6'-trichlorophenyl) -5-pyrazolone Yellow couplers:

46. p-(w-Benzoylacetamino)benzenesulfonamide 47. p (wBenzoylacetamino)benzenesulfon N- methylamide 48.p-(w-Benzoylacetamino)benzenesulfonanilide 49.4-benzenesulfonamino-w-benzoylacetanilide 50. 4(p-toluenesulfonamino)-w-benzoylacetanilide 51. 4(p-laurylbenzenesulfonamino) -w-benzoylacetanilide 52. 1,4-di [p(benzoylacetamino)benzenesulfonaminolbenzene 53. N,N' di(p-benzoylacetaminophenyl)benzene- 1,3-disulfonamide 54. N (pbenzoylacetaminophenyl) -4-[p-(benzoylacetamino)benzenesulfonamido1benzenesulfonamide 55. N -benzoylacetylN-(2-benzothiazo1yl)sulfanilamide 56. pAcetoacetaminobenzenesulfon-fl-naphthalide 5 7.' pFuroylacetaminobenzenesulfon-N-cyclohexylamide 58. p (4ethoxybenzoylacetamino)benzenesulfonamide 59. Terephthaloyl bis[(p-N-amylsulfonamido) acetanilide] 60. p (Quinoline 8 sulfonarnino)-w-benzoylacetanilide 61. p Acetoacetamino-o-methylbenzenesulfon N-anilide 62. N,N' di (pbenzoylacetaminophenol)naphthalene-1,5-disulfonamide 63.p-(Benzenesulfonamino)benzoylacetone 64. N-benzoylaceto-o-anisidineTypical couplers that are primarily useful in the photographic silverhalide emulsion layers of my invention comprise the following:

Coupler:

65. 1 hydroxy-2-[6-(2,4'-di-tert.amylphenoxy) nbutylJ-naphthamide (U.S.Patent 2,474,293) 66. l hydroxy4-phenylazo-4-(p-tert.-butylphenoxy)-2-naphthanilide (U.S. Patent2,521,908) 67. 2(2,4-di-tert.-amylphenoxyacetamino)-4,6-dichloro-S-methylphenol (U.S.Patent 2,725,291) 68. 2 (a di-tert.amylphenoxy-n-butyrylarnino)-4,

6-dichloro-t-methylphenol 69. 6-{oc {4 [OL-'(2,4di-tert.amylphenoxy)butyramido]-phenoxy}acetamido} 2,4 dichloro 3-methylphenol 70. 2 [3-(2",4" diamylphenoxy)acetamidolbenzamido-4-chloro-5-methylphenol 71. 1-(2,4,6trichlorophenyl) 3 [3-(2",4"- di-tert.-amylphenoxyacetamido) benzamido]5- pyrazolone (US. Patent 2,600,788)

72. 1-(2',4,6trichlorophenyl)-3-[3"-(2",4-ditert.-amylphenoxyacetamido)-benzamido]4-(pmethoxyphenyl-azo) -5 -pyrazo1one 6 73. N-(4 benzoyl'acetaminobenzenesulfonyl) N- ('y-phenylpropy1) -p-toluidine (U.S.Patent 2,298,- 443 74. u-o-Methoxybenzoyl-m-chloro 4-[u-(2,4-di-tert.-amylphenoxy) n butyramido] -acetanilide (Mc- Crossen U.S. Patent2,728,658)

75. oc-{3-[oc (2,4-di-tert.amylphenoxy)acetamido-lbenzoyl}-2-rnethoxyacetanilide 76. 3 benzoylacetamido 4methoxy-2',4'-di-tert.-

amylphenoxyacetanilide 77. 4 benzoylacetamido 3-methoxy-2,4-di-tert.-

amylphenoxyacetanilide Other couplers suitable for use in the emulsionsof my invention comprise those disclosed in Spence and Carroll U.S.Patent 2,640,776, issued June 2, 1953; Weissberger et a1. U.S. Patent2,407,210, issued September 3, 1946; and Weissberger et al. U.S. Patent2,474,293, issued June 28, 1949.

The color-forming developers useful in my invention have been previouslydescribed in the prior art, and my invention is not to be restricted tothe use of any particular color-forming developer. The color-forming,developers previously mentioned which I have found to be especiallyuseful in my invention comprise aromatic primary amines containing anamino (substituted or not) or hydroxyl substituent. Phenylenediaminesand substituted derivatives thereof containing a primary amino grouphave been found to provide excellent results when employed incombination with the formamidinothiomethyl compounds of my invention.Typical of such color-forming developers are the sulfonamido substitutedp-phenylenediamines disclosed in Weissberger U.S. Patent 2,548,- 574,issued April 10, 1951, the substituted p-phenylenediamines disclosed inWeissberger et al. U.S. Patent 2,566,- 271, issued August 28, 1951.Other phenylenediamine color-forming developers can be employed to likeadvantage in the process of my invention.

The first developer employed in the process of my invention is generallya rapid developer of the MQ type, i.e., a combination of hydroquinoneand Elon (p-N- methylaminophenyl) developer.

The photographic silver halide emulsions useful in the process of myinvention can be prepared according to known methods, such as thosedescribed in Hewitson and McClintock U.S. Patent 2,618,556, issuedNovember 18, 1952. Of course, emulsions prepared by other methods can beused to equal advantage in my invention. These emulsions can bechemically sensitized or not, as mentioned above. Additional chemicalsensitizers useful in my invention comprise those disclosed in the c0-pending application Serial No. 550,495, filed December 1, 1955 (now U.S.Patent 2,886,437, issued May 12, 1958), in the name of D. E. Piper.

The following examples will serve to illustrate more fully the manner ofpracticing my invention.

Example 1 weight greater than 300 was added to a second portion of thesame emulsion at a concentration of 5 gms. of the oleyl ether per moleof silver halide, and the emulsion coated onto a cellulose acetatesupport. The dried coating was then cut into several strips, identifiedcoating series B below. One strip of each coating was exposed for.second to a SOO-Watt, 3000 K. light source on an -Eastman Type Ibsensitometer. The exposed coatings '7 were then developed for 3 minutesin adevelop'er having the following composition:

Sodium hexametaphosphate g 0.5 Sodium sulfite (anhydrous) g 40.0N-methyl-p-aminophenolsulfate g 5.0 Hydroquinone g-.. 2.0 Sodiumcarbonate (monohydrate) g 25.0 Potassium bromide g 1.0 Potassium iodide(0.1% solution) cc. 2

Water to make one liter. (pH was 10.1 at 70 F.)

The coatings were then washed for two minutes.

Color development.-'Ihe above coatings were given a reversal exposurefor about seconds (flash) with a No. 2 Photoflood set at a distance of52 inches. The coatings were developed to an adequate D-max. in adeveloper having the following formula:

Sulfuric acid (conc.) cc 1.5

2 2,4-dlch1oro-5- (p-toluenesulfonamldo)-1-na.phthol.

The coatings were washed for ten minutes and treated for two minutes ina silver bleach bath having the following composition:

G. Potassium fierricyanide 100 Potassium bromide 10 Borax 7.5

Boric acid a 5.0

Water to make one liter.

The coatings were then treatedfor two minutes in a fixing bath havingthe composition given below, washed and dried. v G. Sodium thiosulfate(pentahydrate) 200 Sodium sulfite (anhydrous) 10 Water to make oneliter.

1n the following table.

Coating Series A Coating Series B Cone, Compound No. g./liter D-max.Cyan D-max. Cyan Fog Fog none 3. 40 0. 18 3. 30 0. 31 0.15 3.10 0. 03 3.30 .06 (b 0. no run no run 3. 16 .08 (c) 0.30 3. 50 .07 2. 90 11 Theimprovement obtained as a result of the use of one of theformamidinothiomethyl compounds of my invention is immediately apparent,in emulsions'with or without a polyethyleneglycol derivative. Whilecolor 8 density is maintained at a high level, the color fog has beenmaterially reduced.

While the advantages of my invention are particularly noticeable in cyandevelopment, they are also quite noticeable in providing improvedresults in magenta and yellow development, as illustrated in thefollowing examples.

Example 2 i In a manner similar to that illustrated in Example 1 above,a portion of a' gelatino-silver-bromiodide emulsion which had beensensitized with a sulfur compound and a gold compound of the typedescribed above, and the oleyl ether of a polyethyleneglycol having amolecular weight greater than 300 (5 g./mole of AgX), was coated on acellulose acetate support. The coating was exposed for second to a-watt, 5400 K. light source on an Eastman Type Ib sensitometer. Theexposed coating was then developed for 4 minutes in a developer havingthe following composition:

Sodium tetraphosphate g 0.5 Potassium bromide g 2.85 Potassium iodide(0.1% solution) cc 15 Sodium bisulfite g 4.2N-methyl-p-aminophenolsu1fate 4.5 Sodium sulfite (anhydrous) g 75.9Hydroquinone g-.. 2.8 Sodium carbonate (monohydrate) g 27.5 Hydroquinonesulfonate g 1.9

Isopropylamine g 6.43 Water to make one liter.

The coating was then washed for two minutes.

Color development.The above coating was given a reversal exposure forabout 10 seconds (flash) with No. 2 Photofloods set at a distance ofabout 60 inches. The coating was developed 2 minutes in a colordeveloper having the following composition:

' G. Sodium hexametaphosphate 0.5 Sodium sulfite 5.0 Color developer 11.5 Sodium carbonate (monohydrate) 20.0 Sodium bromide 0.22 Potassiumiodide .002 6-nitrobenzimidazole nitrate .01 Coupler No. 45 0.5 Sodiumhydroxide 0.7

Water to make one liter.

1 i-amino-3methyl-N,N-diethylanillne hydrochloride.

The coating was washed for 10 minutes and treated for 2 minutes in asilver bleach bath having the composition given above. The coating wasthen rinsed and treated for 2 minutes in a fixing bath having thecomposition given above, washed and dried. A second strip was given thesame treatment except that the flash re-exposure was omitted. The D-max.and color (magenta) fog for the coating were then measured.

Another portion of the same emulsion was treated in exactly the mannerdescribed above, except that compound (a), as identified above, wasadded to the color developer (0.15 g./liter). The D-max. and magenta fogfor this coating were also measured, the following tabulation showingthe comparison between the untreated and treated coatings.

1 Development time-6 minutes.

' Example 3 An ordinary gelatino-silver-bromiodide emulsion sensitizedwith a sulfur sensitizer, a gold compound, and the oleyl ether of apolyethyleneglycol having a molecular weight greater than 300 (5.0g./mole of AgX) was processed in exactly the manner described in Example2 above, except that a yellow color-forming coupler was employed inplace of the magenta developer of Example 2, while the concentration ofcompound (a) was reduced to 0.075 g./ liter for the processing of thesecond coating. The time of color development for the first coating, thecolor developer containing no formamidinothiomethyl compound, was 8minuts, while the development time for the processing of the secondcoating in the color developer containing compound (a) was 30 min- Waterto make one liter.

1 et-amino-3-methyl-N,N-diethylaniline hydrochloride.

Measurement of the D-max. and yellow fog for each of the coatings gavethe following results:

D-max. Yellow Fog Control- 1. 23 0.86 Compound (a) 1. 22 0. 18

While it has been previously proposed to add various mercapto compoundsto color developers, such compounds fail to maintain color density at ahigh level, although they do reduce color fog. For example, processingof an emulsion having the same composition as coating B of Example 1,the same developing compositions shown in Example 1 being used, exceptthat 0.01 g./liter of 1-phenyl-5-mercaptotetrazole was added to thecolor developer in place of the formamidinothiomethyl compound ofExample 1, gave the following results:

Color Cyan Develop- D-max. Fog

ment, min.

Control 4 3. 30 0. 31 1-phenyl-5-mercaptotetrazole 5 1. 42 0.

While the above mercapto compound did reduce the cyan fog to one-thirdthe level of the coating treated with a color developer containing noantifoggant, it also caused a density loss of more than one-half.

While the above examples primarily illustrate the use of photographicemulsions which have been chemically sensitized with the oleyl ether ofpolyethylene glycol, it is to be understood that other condensates ofalkylene oxides can be advantageously employed to sensitize suchemulsions. Such condensates are generally referred to as alkylene oxidepolymers, the alkylene oxides generally containing from 2 to 4 carbonatoms. Such alkylene oxide polymers include polyalkylene glycols andcondensation products of alkylene oxides with organic compoundscontaining an active hydrogen atom, such as alcohols, amines,mercaptans, acids, amides, etc. Generally, such alkylene oxide polymershave a molecular weight of at least 300, as shown in U. S. applicationSerial No. 550,495, mentioned above. It is to be further understood thatthe emulsions employed in my invention need not be chemicallysensitized, although particularly useful results have been obtained withemulsions which have been chemically sensitized with such alkylene oxidepolymers.

The formamidinothiomethyl compounds useful in my invention can be addedto the color developers either in the form of their free bases or in theform of acidaddition salts of these bases. Since the color developingsolutions of my invention are strongly alkaline, the acidaddition saltsare converted to the free bases, in which form they manifest theiractivity. It is to be understood that the term formamidinothiomethylcompound includes not only the free bases but also acid-addition saltsof these bases.

As mentioned above, the compounds of Formula I can be prepared accordingto methods previously described in the prior art. For example, compoundd above was prepared as follows:

Example A.S-carbethoxymethyl 1 phenyl 3 (4H-1,2,4-triaz0l-3-yl)isothiourea 3-amino-1,2,4-triazole was boiled in drydioxane with an equimolecular amount of phenyl isothiocyanate. There wasobtained a 50 to 60 percent yield of the desired1-phenyl-3-(3-triazolyl)thiourea as a white solid which was onlyslightly soluble in water and dioxane, but was readily soluble indimethylformamide. It was recrystallized from its solution indimethylformamide by addition of water to give white crystals melting at230- 234 C.

The above thiourea compound was refluxed for 2 to 4 hours with ethylchloroacetate in dry dioxane, yielding pale yellow solid which meltedgradually with decomposition above 280 C. Recrystallization of thissolid from dimethylformamide yielded S carbethoxymethyl 1- phenyl 3 (4H1,2,4 triazol 3 yl) isothiourea as a solid melting at 296302 C. withdecomposition.

Compound 0 above was prepared according to the directions given in 1our. Am. Chem. Soc, vol. 77 (1955), page 6231.

As mentioned above,"the color-forming compounds of my invention can beprepared according to methods previously described in the literature.The following two examples will serve to illustrate methods of preparingtwo typical couplers useful in my invention.

Example B.N-benzoylaceto-o-anisidine A two-liter flask was fitted with aone-holed rubber stopper and a steam-jacketed Friedrichs condenser. Tothe top of this condenser was fitted a standard distillation head,thermometer and downward pointing Liebig condenser cooled with water.The flask was then charged with 600 cc. of neutral histological xylene,74 g. (0.6 mol.) of o-anisidine and 115 g. (0.6 mol.) of ethylbenzoylacetate. The flask was refluxed for minutes at such a rate thatmost of the boiling xylene condensed in the steam-jacketed condenser,but some distillate was condensed in the cold condenser. The temperatureat the top of the hot condenser was C. at the beginning of the refluxperiod, but slowly dropped to 70 C. at the end of the period. Duringthis time, 45 cc. of distillate was collected from the cold condenser.The heating mantle was turned ofli, 500 cc. of ligroin was added to thehot solution, and the material allowed to cool for 16 hours. Theresulting crystalline product was broken up, filtered olf and air-dried.A yield of 90 g. of crude product was obtained, M.P. 868 C.Recrystallization of the product from 520 cc. of methanol yielded 76.3g. of product, M.P. 86-8 C. Yield was 47.4 percent of theory.

Example C.3- (p-nitrophenoxyacetylamino) -1- (2',4',6'- trichlorophenyl)-5-pyraz0l0ne A two-liter round-bottomed flask equipped with a condenserand a mechanical stirrer, was charged with 450 cc. of acetonitrile, 32g. (0.1 mol.) of 1-(2,4,6-trichlorophenyl)-3-amino-5-pyrazolone (US.Patent 2,600,788),

and 27 g. (0.13 mol.) of p-nitrophenoxyacetyl chloride. The mixture wasrefluxed on the steam bath for three and one-half hours with goodstirring, complete solution occurring when reflux temperature wasattained. At the end of the reflux period, the crystalline product,which had separated from the refluxing mixture, was suctionfiltered fromthe hot mother liquors. It was then washed on the funnel with successiveportions of acetonitrile, ethanol, water, ethanol, and ether. Afterdrying overnight in a steam cabinet, there were obtained 47 g. (89% oftheory) of the desired product as a white solid, M.P. 244-6 C.

The p-nitrophenoxyacetyl chloride used above was prepared as follows: Ina SOD-ml. flask were mixed 19.7 g. (0.1 mole) of p-nitrophenoxyaceticacid and 100 ml. of thionyl chloride. The mixture was refluxed for hourson a steam bath and the excess thionyl chloride removed underreducdpressure. The removal of the thionyl chloride wascontinued untilthe residue had reached constant weight. The acid chloride was usedwithout purification and gave good results. It can be crystallized fromdried ligroin to obtain a white crystalline material melting at 86-87 C.

The p-nitrophenoxyacetic acid used above was prepared as follows: In a5-liter flask were placed 278 g. (2 moles) of p-nitrophenol, 190 g. (2moles) of chloroacetic acid, 168 g. (4.2 moles) of sodium hydroxide and2 liters of water. The mixture was boiled in the open flask until itshowed a neutral reaction to litmus paper. The reaction temperaturereached 115 C. and some water was evaporated. When the neutral point hadbeen reached (2.5-3 hours) an additional 84 g. (2.05 moles) of sodiumhydroxide and 95 g. (1 mole) of chloroacetic acid were added to theflask and the heating continued until a neutral reaction again resulted.

To the cooled reaction mixture were added 500 ml. of concentratedhydrochloric acid with stirring. The solid formed was filtered, slurn'edwith 3 liters of ice cold water and again filtered and washed. with 1.liter of ice cold water. The dry product melted at 182184 C. and weighed300 g. Yield was 76% of the 394 g. theory. It can be crystallized fromdenatured alcohol, if desired.

What I claim as my invention and desire secured by Letters Patent of theUnited States is:

1. A developing composition for color photography comprising anarylenediamine color developer and a compound selected from thoserepresented by the following general formula:

wherein R represents a member selected from the group consisting of ahydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, and amonocyclic aryl group of the benzene series containing from 6 to 7carbon atoms, R represents an amino group, and R represents a memberselected from the group consisting of a carbalkoxyl group containingfrom 2 to 5 carbon atoms, an alkyl group containing from 1 to 4 carbonatoms, a tetrazaindenyl group, a pyridyl group, and an amino carbonylgroup.

2. A developing composition for color photography comprising alkali, analkaline sulfite, a p-phenylenediamine color developer, and a compoundselected from those represented by the following general formula:

group of the benzene series containing from'6 to 7 carbon atoms, Rrepresents an amino group, and R;

represents a'member selected from the group consisting of acarbalkoxylgroup containing from 2 to 5 carbon atoms, an alkyl groupcontaining from '1 to 4 carbon atoms,a tetrazaindenyl group, a pyridylgroup, and an aminocarbonyl group. 4

3. A photographic developer for color photography comprising a stronglyalkaline solution of a p-phenylenediamine photographic developing agent,an alkali metal sulfite and a compound selected from those representedby the following general formula:

wherein R represents a member selected from the group consisting of ahydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, and amonocyclic aryl group of thebenzene series containing from 6 to ,7carbon atoms,"R represents an amino group, and R,representsa'member'selected from the group consisting of a carbalkoxygroup containing from 2 to 5 carbon atoms, an alkyl group containingfrom '1 to 4 carbon atoms, a tetrazaindenyl group, a pyridyl group, andan aminocarbonyl "group.

4. A developing composition for color photography comprising ap-phenylenediamine color developer, an alkali metal sulfite, and acompound selected from those represented by the following generalformula:

wherein R represents a member selected from the group consisting of ahydrogen atom, an alkyl group containing from 1 to 3'carbon atoms, anda'monocyclic aryl group of the benzene series containing from 6 to 7carbon atoms, R represents an amino group, and R represents a memberselected from the group consisting of a carbalkoxyl group containingfrom 2 to 5 carbon atoms, an alkyl group containing from 1 to 4 carbonatoms, a tetrazaindenyl group, 'a pyridyl group, and an aminocarbonylgroup.

5. A developing composition for color photography comprising ap-phenylenediamine color developer, an alkali metal sulfite, and acompound selected from those represented by the following generalformula:

wherein R represents a member selected from the group consisting of ahydrogen atom, an alkyl group containing from 1 to 3 carhon atoms, and amonocyclic aryl group of the benzene series containing from 6 to 7carbon atoms, R represents an amino group, and R represents atetrazaindenyl group.

6. A photographic developing composition for color photographycomprising a p-phenylenediamine color developer, an alkali metalsulfite, and2-formamidinothiomethyl-4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene.

7. A developing composition for color photography comprising ap-phenylenediamine color developer, an alkali metal sulfite, andbis(2-formamidinothiornethyl-G-methyl-l,3,3a,7-tetrazainden-4-yl)sulfide.

8. A developing composition for color photography comprising ap-phenylenediamine color developer, an alkali metal sulfite, and2-S-thiouroniumethanesulfonate.

9. A developing composition for color photography comprising ap-phenylenediamin'e color developer, an alkali metal sulfite, andS-carbethoxymethyl-l-phenyl-3- (4H-1,2,4-triazol-3-yl)isothiourea.

10. A developing composition for color photography comprising ap-phenylenediamine color developing cornpou'nd,'an alkali metal sulfite,a color-forming compound capable of coupling with the oxidation productsof said p-phenylenediamine color developing compound to produce acolored image selected from the group consisting of cyan, magenta andyellow, and a compound selected balkoxyl group containing from 2 to 5carbon atoms, from those represented by the following general formula:an alkyl group containing from 1 to 4 carbon atoms, a

tetrazaindenyl group, a pyridyl group, and an aminocar- I bonyl group.

R 5 wherein R represents a member selected from the group ReferencesCited in the file of this patent consisting of a hydrogen atom, an alkylgroup containing UNITED STATES PATENTS from 1 to 3 carbon atoms, and amonocyclic aryl group of the benzene series containing from 6 to 7carbon gig Mannes et 1941 atoms, R represents an amino group, and Rrepresents 10 3,087 Dersch et a1 1948 a member selected from the groupconsisting of a car- 2,514,650 Knott et July 1950

1. A DEVELOPING COMPOSITION FOR COLOR PHOTOGRAPHY COMPRISING ANARYLENEDIAMINE COLOR DEVELOPER AND A COMPOUND SELECTED FROM THOSEREPRESENTED BY THE FOLLOWING GENERAL FORMULA: